Dissertations / Theses on the topic 'Sol-Gel Dip-Coating'

No presente trabalho foram obtidos e caracterizados filmes finos de SnO2 e SnO2:Sb preparados pelo processo sol-gel. Estes filmes foram estudados através da influência do número de camadas nas suas propriedades ótico-eletroquímicas. Foi observado que a densidade de carga para um filme de SnO2:Sb de 5 camadas foi de 40 mC/cm2, tornando-se um excelente candidato como contra-eletrodo para aplicação em janelas eletrocrômicas. Os filmes de SnO2 e SnO2:Sb também foram estudados utilizando técnicas eletroquímicas: cronoamperometria e voltametria cíclica cujo o enfoque na análise foi o de intercalação de lítio em função da carga inserida. As medidas de transmissão ótica na região de ultravioletainfravermelho próximo revelaram que estes filmes possuem leve coloração azul, evidenciadas pela mudança do espectro UV-Vis em 8% entre estado colorido e descolorido; Por espectroscopia no infravermelho dos sóis, foi possível observar bandas características dos grupos de moléculas presentes em alcóxido, confirmando a formação do alcóxido de estanho enquanto dos precipitados apenas evidências da formação do óxido de estanho. As morfologias dos filmes estudadas por Microscopia Eletrônica de Varredura (MEV) e Microscopia de Força Atômica (AFM) demonstraram que o filme apresenta pequenos riscos, provavelmente devido a presença de Sb, e por AFM obtidas informações da rugosidade e do tamanho de grão, sendo estes valores de 100 nm e 104 nm respectivamente. A partir do espectro do filme por EDX foi possível confirmar a presença de estanho e antimônio nos filmes. A estrutura dos xerogéis e dos sóis para deposição dos filmes estudada por difração de raios-X é a casseterite. Por fim Análises Térmicas (DSC/TGA) demonstram que à 60oC um pico endotérmico correspondendo à liberação de água e uma perda da massa de 6,3 %, e na faixa de 450C um pequeno aumento da linha de base no sentido exotérmico atribuído a cristalização do SnO2:Sb na fase casseterite, com perda de massa de 33%.
In this study were obtained and characterized thin films of SnO2 and SnO2: Sb prepared by the sol-gel process. These films were studied through the influence of the number of layers in its optical-electrochemical properties. It was observed that the density of charge for a film of SnO2: Sb, 5 layers was 40 mC/cm2, making it an excellent candidate as counter-electrode for use in electrochromic windows. The films of SnO2 and SnO2: Sb also were studied using electrochemical techniques: chronoamperometry and cyclic voltammetry with a focus on analysis of intercalation of lithium according to load inserted. Measures of optical transmission in the ultraviolet region of near-infrared revealed that these films have light blue colour, highlighted by the changing spectrum of UV-Vis by 8% between state and colorful discolour; In the infrared spectroscopy, in solution has been possible to see bands characteristics groups of molecules present in alkoxide, confirming the formation of alkoxide of tin while the precipitated only evidence of the formation formation of tin oxide. The morphologies of the films studied by Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM) showed that the film presents little risk, probably because the presence of Sb, and the information obtained by the AFM roughness and the size of grain, and these values of 100 nm and 104 nm respectively. From the spectrum of the film by EDX were unable to confirm the presence of tin and antimony in the films. The structure of xerogel and solution for deposition of films studied by X-rays diffraction is the cassiterite. Finally Thermal Analysis (DSC / TGA) show that the 60oC a peak endothermical corresponding to the release of water and a loss of the mass of 6.3%, and in the 450ºC a small increase from baseline in the sense attributed range of exothermically the crystallization of SnO2:Sb during casseterite, with mass loss of 33%.

Negli impianti utilizzati per la produzione di energia elettrica che sfruttano l'energia solare, quali la tecnologia solare a concentrazione (Solare Termodinamico) sviluppata da ENEA, per minimizzare le dispersioni di calore è necessaria una elevata selettività spettrale. Per ottimizzare l'efficienza dell'impianto è quindi necessario lo sviluppo di materiali innovativi, in grado di minimizzare la quantità di energia dispersa per riflessione. In questo studio, per incrementare la trasmittanza solare dei componenti in vetro presenti nei tubi ricevitori dell'impianto, sono state utilizzate tipologie diverse di rivestimenti antiriflesso (multistrato e a singolo strato poroso). I rivestimenti sono stati ottenuti mediante via umida, con tecnica di sol-gel dip-coating. I sol coprenti sono stati preparati da alcossidi o sali metallici precursori degli ossidi che costituiscono il rivestimento. Sono state approfondite sia la fase di sintesi dei sol coprenti, sia la fase di deposizione sul substrato, che ha richiesto la progettazione e realizzazione di una apparecchiatura prototipale, ossia di un dip-coater in grado di garantire un accurato controllo della velocità di emersione e dell'ambiente di deposizione (temperatura e umidità). Il materiale multistrato applicato su vetro non ha migliorato la trasmittanza del substrato nell'intervallo di lunghezze d'onda dello spettro solare, pur presentando buone caratteristiche antiriflesso nell'intervallo dell'UV-Vis. Al contrario, l'ottimizzazione del rivestimento a base di silice porosa, ha portato all'ottenimento di indici di rifrazione molto bassi (1.15 to 1.18) e ad un incremento della trasmittanza solare dal 91.5% al 96.8%, efficienza superiore agli attuali rivestimenti disponibili in commercio.

Negli impianti utilizzati per la produzione di energia elettrica che sfruttano l'energia solare, quali la tecnologia solare a concentrazione (Solare Termodinamico) sviluppata da ENEA, per minimizzare le dispersioni di calore è necessaria una elevata selettività spettrale. Per ottimizzare l'efficienza dell'impianto è quindi necessario lo sviluppo di materiali innovativi, in grado di minimizzare la quantità di energia dispersa per riflessione. In questo studio, per incrementare la trasmittanza solare dei componenti in vetro presenti nei tubi ricevitori dell'impianto, sono state utilizzate tipologie diverse di rivestimenti antiriflesso (multistrato e a singolo strato poroso). I rivestimenti sono stati ottenuti mediante via umida, con tecnica di sol-gel dip-coating. I sol coprenti sono stati preparati da alcossidi o sali metallici precursori degli ossidi che costituiscono il rivestimento. Sono state approfondite sia la fase di sintesi dei sol coprenti, sia la fase di deposizione sul substrato, che ha richiesto la progettazione e realizzazione di una apparecchiatura prototipale, ossia di un dip-coater in grado di garantire un accurato controllo della velocità di emersione e dell'ambiente di deposizione (temperatura e umidità). Il materiale multistrato applicato su vetro non ha migliorato la trasmittanza del substrato nell'intervallo di lunghezze d'onda dello spettro solare, pur presentando buone caratteristiche antiriflesso nell'intervallo dell'UV-Vis. Al contrario, l'ottimizzazione del rivestimento a base di silice porosa, ha portato all'ottenimento di indici di rifrazione molto bassi (1.15 to 1.18) e ad un incremento della trasmittanza solare dal 91.5% al 96.8%, efficienza superiore agli attuali rivestimenti disponibili in commercio.

Ce travail s’intéresse a la synthèse et à la caractérisation de revêtements hybrides O/I à base de silice, préparés par voie sol-gel et déposés sur polycarbonate (PC), pour des applications en milieu chaud et humide dans le domaine culinaire. Le PC étant connu pour sa sensibilité à l’hydrolyse dans ce type de milieux (provoquant sa dépolymérisation progressive et ainsi la libération de bisphénol A, molécule suspectée comme étant toxique), le rôle du revêtement est donc de protéger le PC et d’éviter son vieillissement prématuré, tout en améliorant ses propriétés mécaniques. Dans un premier temps, de nombreux sols ont été synthétisés et optimisés, principalement en termes de nature et quantités de précurseurs, et de pH, dans le but d’obtenir des revêtements homogènes et transparents. Un suivi des réactions d’hydrolyse et de condensation des sols a également été réalisé afin de déterminer le temps minimal de maturation de ces derniers. Apres dépôt des revêtements par dip-coating, les propriétés mécaniques des films ont été étudiées par de nombreuses techniques. D’un point de vue général, les propriétés des échantillons revêtus ont été trouvées supérieures à celles du PC nu. L’influence de nombreux paramètres de synthèse comme le ratio organoalcoxysilane(s)/silice colloïdale, l’ajout d’additifs, le type de traitement de surface du PC pré-dépôt ou encore les conditions de recuit, a également été étudiée. L’ensemble de ce travail a permis d’obtenir, à partir de deux systèmes sol-gel différents, des revêtements performants en termes de transparence, d’adhésion au substrat, de non-toxicité, couplés à des valeurs élevées de dureté, de densité et de module de Young
This work deals with the synthesis and the characterization of hybrid O/I silica coatings prepared by the sol-gel route and deposited on polycarbonate (PC), for applications in hot and humid environment in the alimentary field. PC is well-known for undergoing hydrolysis in such conditions (causing its progressive depolymerization and thus leading to the release of bisphenol A, a molecule suspected to be toxic): the function of the coating would thus consist in preventing PC from this kind of premature ageing, along with the enhancement of its mechanical properties. As a first step, a lot of different sols were synthesized and optimized, mainly in terms of type and quantity of precursors, along with the pH, in order to obtain transparent and homogeneous coatings. The hydrolysis and condensation reactions were monitored in order to determine the minimum ageing time to be waited before any film deposition. After deposition by dip-coating, the mechanical properties of the films were assessed by using many different techniques. Basically, the coated-PC samples display higher properties than the uncoated one. The influence of numerous synthesis parameters such as the organoalkoxysilanes/colloidal silica ratio, the presence of additives, the kind of surface treatment of PC before film deposition, or the annealing conditions was also studied. This whole work led to the synthesis, from two different sol-gel systems, of superior quality coatings in terms of transparency, adherence to the substrate, non-toxicity, along with elevated hardness, density and Young’s modulus values

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Neste trabalho foi realizada a simulação numérica da fase líquida no processo de deposição de filmes finos pela técnica de molhamento (dip-coating), via sol-gel, utilizando como aplicação soluções precursoras de dióxido de estanho (Sn'IND. 2'). Dióxido de estanho é um semicondutor transparente de gap largo, amplamente utilizado em muitos tipos de dispositivos. Além da técnica convencional, o trabalho analisa uma nova proposta da técnica de deposição dip-coating onde a solução se encontra em uma temperatura diferente da ambiente. Para ambas as técnicas foram realizadas a modelagem matemática dos problemas e desenvolveu-se um método numérico apropriado baseado no método MAC (Marker and Cell). O problema foi resolvido em coordenadas cartesianas bidimensionais e as equações foram discretizadas pela técnica de diferenças finitas. Os resultados numéricos são visualizados por meio da distribuição de temperatura e vetores velocidade da solução precursora, que fornecem subsídios para investigação da influência dos vetores velocidade na obtenção de filmes com boas propriedades, em relação à uniformidade e homogeneidade. Verifica-se que estas características refletem diretamente na qualidade óptica dos filmes investigados, tornando-se parâmetros importantes para aplicações em dispositivos opto-eletrônicos. Através dos resultados numéricos verificou-se que nas regiões do fluido próximas ao substrato, os módulos dos vetores velocidade são maiores, há uma maior quantidade de material sendo depositado. Notou-se também, através da distribuição de velocidades em direção ao substrato que o filme tem uma melhor uniformidade na sua espessura quando os vetores velocidade possuem os valores de seus módulos mais próximos uns dos outros. Portanto, mudando os parâmetros iniciais de viscosidade, densidade, velocidade de imersão/emersão do substrato ou temperatura no fluido pode-se estudar o comportamento.
In this work, the numerical simulation of liquid phase in the thin film deposition, by the sol-gel-dip-coating technique, was carried out. The method was applied to tin dioxide (Sn'IND. 2') solutions. Tin dioxide is a transparent semiconductor of wide bandgap, extensively used in many types of devices. Besides the conventional procedure, this work analyses a new proposal for the deposition technique, where the solution is heated above room temperature. In both cases, the mathematical modeling was done and the appropriated numerical method was developed, based on MAC (Marker and Cell) approach. The problem was solved in two-dimensional Cartesian coordinates and the equations were discretized by the finite difference technique. The numerical results are visualized through temperature and vector velocity distributions in the precursos solution, yielding subsides to the investigation of the influence of vectors velocity in the deposition of good property films, concerning uniformity and homogeneity. It was verified that these characteristics point directly toward the optical quality of investigated films, becoming important parameters for application in optoelectronic devices. The numerical results allow verifying that in the fluid regions close to the substrate, where the velocity modulus is highter, there is a larger amount of material being deposited. It was also noticed, through the velocity distribution towards the substrate, that the film has a better thickness uniformity when the vectors velocity have modulus values closer to each other. Therefore, changing initial parameters such as viscosity, density, substrate dipping rate or fluid temperature, it is possible to evaluate the fluid behavior during the thin film deposition.

Filmes hidrofóbicos são caracterizados por repelir soluções aquosas quando em contato com superfícies revestidas ou com algum material que possua propriedades hidrofóbicas. Estes materiais têm despertado a atenção tecnológica devido às propriedades de: auto-limpeza, anti-gelo, anti-aderente e anti-corrosão. Este trabalho teve como objetivo a obtenção do filme hidrofóbico, em temperatura ambiente, utilizando o silano viniltrietoxisilano (VTES) sobre chapas de aço inoxidável AISI 204 em solução sol-gel pelo processo de dip-coating, tendo como finalidade o aumento da resistência à corrosão do substrato metálico. Para a reação de hidrólise foi preparada uma solução com relação percentual de silano/etanol/água de 4/48/48% em volume. Alguns parâmetros da solução e da superfície do substrato foram variados, tais como o tempo de hidrólise do silano na solução sol, em 2 e 24 horas, e a rugosidade do substrato pelo processo de jateamento com micropartículas de óxido de alumina comparando-o com o substrato liso (sem modificações). O filme foi caracterizado por microscopia eletrônica de varredura (MEV), ângulo de contato (CA), espectroscopia no infravermelho por transformada de Fourier (FTIR), espectroscopia de impedância eletroquímica (EIE), polarização potenciodinâmica, espectroscopia de energia dispersiva de raios-x (EDS), névoa salina e câmara úmida. Através destas técnicas de caracterização, pode-se avaliar a resistência à corrosão, a homogeneidade e a hidrofobicidade do filme obtido. Os resultados da influência do tempo de hidrólise demonstram que a solução de 24 horas proporciona um aumento na hidrofobicidade do filme de 12° em relação à solução de 2 horas de hidrólise. Enquanto que, a modificação da superfície com o jateamento favorece um aumento de 36° no ângulo de contato em relação à superfície lisa. Os ensaios eletroquímicos mostram que o substrato que possui maior ângulo de contato, 130°, apresenta maior resistência a corrosão comparando-o com as outras amostras, as quais apresentam ângulos de contato menores. Porém, os resultados de névoa salina comprovam que as amostras com a superfície lisa, ângulo de contato de 90°, possuem maior durabilidade do que as amostras jateadas quando expostas a ambientes salinos. Conclui-se que a metodologia utilizada é eficaz para a obtenção de revestimentos hidrofóbicos e para a proteção do metal base contra à corrosão.
Hydrophobic films are characterized to repel water or aqueous solutions when in interaction with coated surfaces or any materials with hydrophobic properties. These materials have attracted attention due the technological properties, like: self-cleaning, anti-icing, anti-adherent and anti-corrosion. This study aimed to obtain the hydrophobic film at room temperature using the vinyltriethoxysilane (VTES) on stainless steel AISI 204 in sol-gel solution by dip-coating process, with the purpose to increase the corrosion resistance of metal substrate. The hydrolysis reaction was prepared a solution with a percentage ratio of silane/ethanol/water 4/48/48% in volume. Some parameters of the solution and the substrate surface were varied, such as silane hydrolysis time in the sol solution at 2 and 24 hours, and the roughness of the substrate by blasting process with microparticles of aluminum oxide and it was compared with the smooth substrate (unchanged). The film was characterized by scanning electron microscopy (SEM), contact angle (CA), infrared spectroscopy by Fourier Transform (FTIR), electrochemical impedance spectroscopy (EIS), potentiodynamic polarization, energy dispersive spectroscopy (EDS), salt spray and humid room tests. Through these characterization was possible to evaluate the corrosion resistance, uniformity and hydrophobicity of the film developed. The influence of hydrolysis time showed an increase in contact angle of 12° when used the 24 hours of hydrolysis solution in relation to 2 hours of hydrolysis. While the surface modification using the blasting tecnique favors an increase of 36° in contact angle in comparison to the smooth surface. Between the samples evaluated by electrochemical spectroscopy, proves the higher contact angle, 130°, has best performance in corrosion resistance compared with another samples studied which have lower contact angles. However, the smooth substrate, contact angle 90°, showed the best performance in salt spray test compared to rough surfaces samples. The methodology developed was effective to obtain hydrophobic coatings and protection the metal substrate against the corrosion.

L'oxyde de nickel est l'un des matériaux électrochromes les plus utilisés dans le domainedes fenêtres intelligentes qui contrôlent la lumière et la chaleur provenant de l'extérieur versl'intérieur des bâtiments. Il est important de mentionner que l’oxyde de nickelstoechiométrique est un isolant à température ambiante. Les propriétés microstructurales,chimiques, optiques et électrochromes des couches minces dépendent fortement du procédéde préparation et traitement final. En outre, l’un des principaux défis consiste à fabriquer lescouches minces sur des substrats souples afin de fabriquer des fenêtres électrochromes degrande taille ce qui demande un traitement à T ambiante. A cet égard peu d’étudesbibliographiques ont évalué l’effet du traitement par les rayonnements UV sur les propriétésdes couches électrochromes. Dans ce travail, des couches minces d'oxyde de nickel (NiO) ontété préparées par la méthode Sol-Gel associée aux techniques de dépôts par centrifugation(spin-coating) et par trempage-retrait (dip-coating). L’ajustement des paramètresexpérimentaux relatifs à ce procédé (la concentration du précurseur, la nature du solvant et dustabilisant, le nombre de couches déposées et le type des traitement final (calcinationà 300 °C ou traitements UV) a permis d’optimiser les conditions de préparation des couchesminces et par la suite de contrôler les caractéristiques chimiques, microstructurales et optiquesdes couches développées. Cette étude a montré qu'une concentration de 0,3 M d'acétate denickel, le méthanol comme solvant et le triton X-100 en tant que stabilisant conduisent à unecouche mince NiO avec les meilleures performances optiques. Les caractérisations par lestechniques (DRX, ATG, FT-IR, XPS et GDOES) ont particulièrement mis en évidence le rôledes conditions de traitement final sur la composition et la morphologie des couches d’oxydede nickel élaborées. La DRX a montré qu’elles sont faiblement cristallisées et que la structuredevient plus amorphe avec le traitement UV. La spectrométrie UV-visible et les CV ont révéléque les couches traitées par UV en utilisant une lampe de 30 W pendant 5 h (UV-30W-5h)possèdent le contraste optique le plus élevé et la meilleure stabilité électrochimique. L'analysemorphologique a montré que les couches minces déposées par la technique de spin coatingsouffrent de la formation de fissures et d’une hétérogénéisation de la surface. Pour résoudre ceproblème, le procédé de spin-coating a été remplacé par la technique dip-coating tout enconservant les paramètres optimisés précédemment. Cette technique a permis de produire descouches minces plus homogènes et moins fissurées. D'autre part, pour continuer à améliorerles propriétés électrochromes, ces couches ont été dopées par le lithium. Les résultats obtenusont montré l’importance de l’addition de Li sur l’amélioration des propriétés électrochromesde Li : NiO cyclé dans KOH comme électrolyte. En effet, une variation de la transmittanceΔT de 70% (à 450 nm) a été obtenue dans les couches minces 8 % Li: NiO. Le résultat quiressort des caractérisations FT-IR et ATG, porte sur le fait que les couches calcinéescontiennent moins de composés organiques, à l’inverse de celles traitées par UV riches enmatière organique. L'analyse XPS a montré que la teneur en Ni2+ est plus élevée dans lescouches dopées. L’analyse GDOES a montré une distribution homogène de Li dans toutel’épaisseur de la couche. Toutefois, les couches minces de 8% de Li: NiO traitées par UV-30W-5h souffrent d’une dégradation de leurs performances électrochromes dans le KOHaprès quelques cycles, pour cette raison, elles ont été cyclées dans d’autres électrolytesliquides ioniques, tels que le LiTFSI-EMITFSI, le NaTFSI-EMITFSI et le KTFSI-EMITFSI.Les meilleures propriétés électrochromiques ont été obtenues avec l'électrolyte KTFSIEMITFSI.Ce résultat important représente une bonne perspective pour l'avenir
Nickel oxide is one of the most widely used electrochromic materials in the field of smartwindows that control light and heat from the outside to the inside of buildings. It is importantto mention that stoichiometric nickel oxide is an insulator at room temperature. Themicrostructural, chemical, optical and electrochromic properties of the films are highlydependent on the process of preparation and final treatment. In addition, one of the mainchallenges is the elaboration of thin films on flexible substrates suitable for electrochromicapplications which requires treatment at ambient T. In this respect, in literature, few studieshave reported the effect of UV treatment on the properties of electrochromic layers. In thiswork, thin films of nickel oxide (NiO) were prepared by the Sol-Gel method associated withspin-coating and dip-coating techniques. The adjustment of the experimental parametersrelating to this process (the concentration of the precursor, the nature of the solvent and thestabilizer, the number of deposited layers and the type of final treatment (calcination at300 °C or UV treatments) made it possible to optimize conditions for the preparation of thinlayers and subsequently to control their chemical, microstructural and optical characteristics.This study showed that a concentration of 0.3 M nickel acetate, methanol as solvent and triton100-X as a stabilizer lead to NiO thin film with the highest optical properties. The techniquesof characterizations (DRX, ATG, FT-IR, XPS and GDEOS) have particularly highlighted therole of the final treatment conditions on the composition and the morphology of the preparednickel oxide thin films. The XRD results showed that they are weakly crystallized and thestructure becomes even more amorphous for UV treated samples. UV-visible spectrometryand cyclic voltammetry revealed that UV-treated thin films using a lamp of 30 W for 5 h(UV-30W-5h) have the highest optical contrast and the highest electrochemical stability.Morphological analysis (SEM) indicated that the thin films deposited by the spin-coatingtechnique suffer from crack formation and surface heterogenization. To solve this issue, thespin-coating process has been replaced by the dip-coating technique while retaining thepreviously optimized parameters. This technique has made it possible to produce thin filmsthat are more homogeneous and less cracked. On the other hand, to continue to improve theelectrochromic properties, these thin films were doped with lithium. The results showed theimportance of the addition of Li on the improvement of the electrochromic properties ofLi : NiO cycled in KOH as electrolyte. Indeed, a variation of the ΔT transmittance of 70 %was reached for the thin films 8 % Li : NiO. The result of the FT-IR and ATGcharacterizations showed that the calcined thin films contain lesser amount of organiccompounds compared to those treated by UV which still contains large amount of organicmatter. XPS analysis has shown that the Ni2+ content is higher in the doped layers. GDOESanalysis showed a homogeneous distribution of Li along the thickness of the thin film.However, 8% Li: NiO thin films treated with UV-30W-5h suffer from a degradation of theirelectrochromic performances in KOH after a few cycles. For this reason, their cyclingproperties have been investigated in a large range of electrolytes, based on ionic liquidincluding LiTFSI-EMITFSI, NaTFSI-EMITFSI and KTFSI-EMITFSI. The highestelectrochromic properties were obtained with KTFSI-EMITFSI as an electrolyte. Thisimportant result presents a good prospect for the future

Avec une industrialisation mondiale en croissance continue atteignant 6,1% en 2021 et un fardeau démographique de 8 milliards de personnes, le monde d'aujourd'hui est confronté aux pénuries d'énergie les plus importantes et à la pollution environnementale la plus étendue de son histoire. Particulièrement, les effluents chargés de molécules toxiques organiques récalcitrantes provenant des raffineries, de l'industrie pétrochimique, pharmaceutique, des plastifiants et de nombreuses autres industries mettent en danger la durabilité des eaux de surface et des eaux souterraines. Avec l'inefficacité des techniques de traitement conventionnelles pour résoudre ce problème, les processus d'oxydation avancée (AOP) sont apparus comme une technologie efficace, prometteuse et peu coûteuse, capable de s'attaquer à différents types de molécules organiques dans les milieux aquatiques. Parmi ces techniques, la photocatalyse hétérogène est apparue comme l'une des méthodes les plus efficaces et économiques en raison de la réutilisabilité du photocatalyseur et de l'absence de besoins en matière d'élimination secondaire. La technique est basée sur la génération d'espèces d'oxygène hautement réactives (ROS) lors de l'exposition d'un matériau photocatalytique à la lumière, conduisant à une technologie verte et durable. Ces ROS sont bien connus pour leur forte capacité d'oxydation de la matière organique, conduisant à leur minéralisation en molécules d’eau et dioxyde de carbone. Pour cette raison, le développement d'un photocatalyseur efficace et respectueux de l'environnement est important. Dans ce contexte, l'oxyde de zinc (ZnO) a attiré une grande attention à cause son efficacité élevée de conversion de l'énergie photonique, de son faible coût de production, de son faible degré de toxicité pour la vie marine/humaine et de sa longue durée de vie. Cependant, l'un des principaux défis auxquels ce matériau est confronté est l'efficacité photocatalytique limitée en raison de la recombinaison des paires électron-trou. Par conséquent, de nouvelles stratégies ont été développées pour améliorer son activité photocatalytique, telles que la conception de nouvelles micro/nanostructures de ZnO ou le couplage des photocatalyseurs avec d'autres techniques de traitement pour produire des effets synergiques. L'objectif de cette thèse est de concevoir de nouveaux types de nanostructures de ZnO pour dégrader efficacement les contaminants toxiques en phase liquide ou gazeuse. Pour cette raison, l'impact de la structure chimique des polluants sur la cinétique de dégradation a d'abord été étudié sur diverses molécules organiques toxiques. Ensuite, le système photocatalytique a été adapté pour la photodégradation de particules de microplastiques d'une taille de 300 μm. Les effets de la morphologie et de la microstructure sur l'activité photocatalytique du ZnO ont été étudiés afin d'améliorer l'efficacité du système photocatalytique. Pour y parvenir, des nanobâtonnets, des couches minces poreuses et plissées ont été synthétisés en optimisant les techniques de sol-gel et de croissance hydrothermale en milieu liquide. Bien que les nouveaux matériaux aient montré une cinétique de dégradation améliorée, le taux de recombinaison rapide des paires electron-trou continuait néanmoins de freiner son activité photocatalytique. Pour surmonter cette limitation, une oxydation photo-Fenton-like a été couplée au photocatalyseur ZnO. Quand les deux processus fonctionnant simultanément, un effet synergique a été obtenu grâce à la diminution de la recombinaison électron-trou d'un côté, et la régénération du réactif Fenton de l'autre côté. De plus, une nouvelle matrice de ZnO macroporeuses a été conçue en couplant la chimie sol-gel avec l'auto-assemblage de copolymères en bloc. Le nouveau matériau a présenté des propriétés d'auto-nettoyage remarquables lorsqu'il a été appliqué sur des surfaces revêtues
With a continuously growing global industrialization reaching 6.1% in 2021 and a demographic burden of 8 billion people, today’s world is facing the most extensive energy shortages and environmental pollution in its history. Particularly, loaded effluents with recalcitrant organic toxic molecules from refineries, petrochemicals, pharmaceuticals, plasticizers, and many other industries, are continuously endangering surface and groundwater water sustainability. With the low efficiency of conventional treatment techniques in addressing this issue, advanced oxidation processes have emerged as an efficient, promising, and inexpensive technology, capable of tackling different types of organic molecules in aquatic mediums. Amongst these techniques, heterogeneous photocatalysis has emerged as one of the most efficient and economical methods due to the photocatalyst reusability and lack of secondary disposal requirements. The technique is based on the generating of highly reactive oxygen species (ROS) such as hydroxyl radical and superoxide radical upon the exposure of a photocatalyst material to light, making it a green and sustainable technology. These ROS are well-known for their strong oxidation capacity toward organic matter, leading to their mineralization into harmless molecules such as water and carbon dioxide. For that reason, developing an efficient and eco-friendly photocatalyst is of great importance. In this scope, Zinc oxide (ZnO) has been attracting high attention due to its high conversion efficiency of photonic energy, low production price, low degree of toxicity to marine/human life, and long life span. Nonetheless, one of the main challenges facing this material is the limited photocatalytic efficiency due to the recombination of electron-hole pairs. Therefore, new strategies have been developed to enhance its photocatalytic activity such as designing new micro/nanostructures of ZnO or coupling the photocatalysts with other treatment techniques to produce synergic effects

Este trabalho investigou a obtenção de filmes de TiO2 por sol-gel e dipcoating (SGDC) e sua caracterização microestrutural e como fotocatalisador para a produção de hidrogênio a partir da água. Os precursores e reagentes utilizados foram: propóxido de titânio, ácido acético, etanol anidro, acetilacetona, Triton X-100 e polivinilbutiral (PVB). Foram preparadas 2 soluções precursoras, uma com PVB e outra sem. Foram produzidos filmes com 1, 2 e 3 camadas através da técnica de dip-coating. Os filmes foram tratados termicamente a 400, 500 e 600ºC, com uma taxa de 100ºC/h e um patamar de 2 h. O TiO2 sintetizado e os filmes produzidos foram caracterizados por difração de raios X (DRX) quanto à cristalinidade, fases presentes e tamanho de cristalito; microscopia eletrônica de varredura (MEV), adsorção de nitrogênio (método BET), análises termogravimétricas (ATG) e termodiferenciais (ATD), elipsometria espectroscópica, perfilometria óptica, espectroscopia Raman e de reflectância difusa (determinação do band gap). Após o tratamento térmico os filmes apresentaram uma microestrutura bastante irregular e com muitas trincas, com a presença da fase anatase em todas as temperaturas de tratamento térmico, e um teor de 3,7% de rutilo à 600ºC. O band gap dos filmes aumentou com a quantidade de camadas adicionadas, com a elevação da temperatura de tratamento térmico e adição de PVB. As medidas de fotocorrente foram realizadas no escuro e sob iluminação de lâmpada de Xe com 250W (simulador de luz solar de 1,5AM). A maior fotocorrente medida foi de 12 μA a 0,5V. A produção de H2 aumentou linearmente com o tempo de exposição para ambas as amostras com PVB. Foi possível relacionar a adição do PVB com o favorecimento da fotoatividade dos filmes de TiO2.
This work has investigated the effect of polyvinyl butyral addition in the synthesis of TiO2 films by sol-gel and dip-coating, their microstructural features and their photoelectrochemical activity for water-splitting hydrogen production. The precursors and reagents used were: titanium propoxide, acetic acid, anhydrous ethanol, acetylacetone, Triton X-100 and polyvinyl butyral (PVB). Two precursor solutions were prepared: one with PVB and another without it. The dip-coating technique was used to produce films with 1, 2 and 3 layers. The films were heat treated at 400, 500 and 600ºC, at a rate of 100°C/h and dwelling time of 2h. Afterwards the synthesized films were characterized by X-ray diffraction (XRD); scanning electron microscopy (SEM), nitrogen adsorption (BET method), thermogravimetric (TGA) and differential thermal analysis (DTA), spectroscopic ellipsometry, optical profilometry, Raman and diffuse reflectance spectroscopy (determination of the band gap). The films after heat treatment showed a very irregular microstructure with many cracks. The anatase phase was presented in all temperatures and a small content of rutile at 600 °C (around 3.7%) was identified. The band gap of the films increased with the number of layers, heat treatment and addition of PVB. The photocurrent measurements were carried out in the dark and under illumination with 250W Xe, using a sunlight simulator (1,5AM). The highest photocurrent was 12A at 0.5V. The H2 production increased linearly with time of exposure for both samples with PVB. Therefore, it was possible to relate the addition of PVB with improvement the photoactivity of TiO2 films.

L’objectif de ce travail a été d’étudier des matériaux semiconducteurs de type p comme photocathode pour la réduction de protons dans le cadre de la photoélectrolyse de l’eau. Ainsi, deux types de matériaux ont été étudiés, des oxydes de cuivre, Cu2O et CuO, et des matériaux à structure pérovskite (ATiO3, A=Ca, Ba, Sr) dopées au fer et à l’azote. Les oxydes de cuivre ont été synthétisés par deux voies différentes afin d’obtenir des films : par voie sol-gel couplée au dip-coating et par électro-dépôt et anodisation du cuivre. La photocorrosion des oxydes de cuivre en milieu aqueux et sous illumination a été mise en évidence. La protection des oxydes de cuivre via une hétérojonction avec un semiconducteur de type n (TiO2 ou BaTiO3) a révélé une meilleure stabilité des électrodes au cours du temps ainsi que des photocourants élevés grâce à une composition et une architecture originales. Les pérovskites ont été synthétisées par voie sol-gel couplée au dip-coating. Ce sont des semiconducteurs de type n ; ainsi l’étude du dopage au fer, pour substituer le titane, et à l’azote, pour substituer l’oxygène, a mis en évidence un changement de nature de type n à type p, ainsi qu’une diminution de la largeur de bande interdite. Les propriétés physico-chimiques de toutes les électrodes synthétisées ont été caractérisées (structure cristalline, morphologie, propriétés optiques et électrochimiques) et discutées en fonction de leur composition et des paramètres de synthèse. Ces travaux ont permis d’élaborer des photocathodes originales, performantes et stables au cours du temps (oxydes de cuivre protégées), et de démontrer l’utilisation de pérovskites dopées pour cette application
The aim of this work was to study p-type semiconducting materials as photocathodes for protons reduction into H2 for water splitting application. Two types of materials have been studied: copper oxides, Cu2O and CuO, and materials with a perovskite structure (ATiO3, A=Ca, Ba, Sr) doped by iron and nitrogen. Copper oxides have been synthetized by two different ways in order to obtain films: sol-gel process coupled with dip-coating and copper plating and anodization. Copper oxides photocorrosion has been highlighted in aqueous environment and under illumination. Their protection via a heterojunction with an n-type semiconductor (TiO2 and BaTiO3) improved electrodes stability over time and photocurrents, thanks to original composition and architecture. Perovskites have been synthetized by sol-gel process coupled with dip-coating. They are well-known as n-type semiconductors; so the study of doping with iron, to substitute titanium, and with nitrogen, to substitute oxygen, shows a change from n-type to p-type, and a reduction of the band gap. The physical and chemical properties of the synthetized electrodes were characterized (crystal structure, morphology, optical and photoelectrochemical properties) and discussed according to the composition and synthesis parameters. This work enables to obtain original, efficient, and stable over time, photocathodes (protected copper oxides) and to demonstrate the potential use of doped perovskites for this application

Transparent conducting oxide (TCOs) thin films, including non-stoichiometric tin doped indium oxide (ITO) and aluminium doped zinc oxide (AZO), have found considerable applications in various displays, solar cells, and electrochromic devices, due to their unique combination of high electrical conductivity and optical transparency. TCO thin films are normally fabricated by sputtering, thermal vapour deposition and sol-gel method. Among them, sol-gel processing, which was employed in this project, is no doubt the simplest and cheapest processing method, The main objectives of this project were to produce indium tin oxides (ITO) and zinc aluminium oxides (AZO) nanoparticles with controlled particle size and morphology and to fabricate TCO thin films with high optical transmittance and electrical conductivity. In this research, hydrothermal method was used to synthesise ITO and AZO nanoparticles. Tin oxides, zinc oxides, ITO and AZO particles with the particle size ranging from 10 nm to several micrometers and different morphologies were synthesised through controlling the starting salts, alkaline solvents and hydrothermal treatment conditions. ITO and AZO thin films were fabricated via sol-gel technique through dip coating method. The effects of the starting salts, alkaline solvents, surfactant additives and coating and calcination conditions on the formation of thin films were investigated. XRD, TEM, FEG-SEM, DSC-TGA, UV-Vis spectrometer and four-point probe resistance meter were used to characterise the crystallinity, particle size, morphology, optical transmittance and sheet resistance of the particles and thin films. Crack-free thin films with high optical transmittance (>80% at 550 nm) and low sheet resistances (2.11 kΩ for ITO and 26.4 kΩ for AZO) were obtained in optimised processing conditions.

L’objectif de ce travail a été d’étudier des matériaux semiconducteurs de type p comme photocathode pour la réduction de protons dans le cadre de la photoélectrolyse de l’eau. Ainsi, deux types de matériaux ont été étudiés, des oxydes de cuivre, Cu2O et CuO, et des matériaux à structure pérovskite (ATiO3, A=Ca, Ba, Sr) dopées au fer et à l’azote. Les oxydes de cuivre ont été synthétisés par deux voies différentes afin d’obtenir des films : par voie sol-gel couplée au dip-coating et par électro-dépôt et anodisation du cuivre. La photocorrosion des oxydes de cuivre en milieu aqueux et sous illumination a été mise en évidence. La protection des oxydes de cuivre via une hétérojonction avec un semiconducteur de type n (TiO2 ou BaTiO3) a révélé une meilleure stabilité des électrodes au cours du temps ainsi que des photocourants élevés grâce à une composition et une architecture originales. Les pérovskites ont été synthétisées par voie sol-gel couplée au dip-coating. Ce sont des semiconducteurs de type n ; ainsi l’étude du dopage au fer, pour substituer le titane, et à l’azote, pour substituer l’oxygène, a mis en évidence un changement de nature de type n à type p, ainsi qu’une diminution de la largeur de bande interdite. Les propriétés physico-chimiques de toutes les électrodes synthétisées ont été caractérisées (structure cristalline, morphologie, propriétés optiques et électrochimiques) et discutées en fonction de leur composition et des paramètres de synthèse. Ces travaux ont permis d’élaborer des photocathodes originales, performantes et stables au cours du temps (oxydes de cuivre protégées), et de démontrer l’utilisation de pérovskites dopées pour cette application
The aim of this work was to study p-type semiconducting materials as photocathodes for protons reduction into H2 for water splitting application. Two types of materials have been studied: copper oxides, Cu2O and CuO, and materials with a perovskite structure (ATiO3, A=Ca, Ba, Sr) doped by iron and nitrogen. Copper oxides have been synthetized by two different ways in order to obtain films: sol-gel process coupled with dip-coating and copper plating and anodization. Copper oxides photocorrosion has been highlighted in aqueous environment and under illumination. Their protection via a heterojunction with an n-type semiconductor (TiO2 and BaTiO3) improved electrodes stability over time and photocurrents, thanks to original composition and architecture. Perovskites have been synthetized by sol-gel process coupled with dip-coating. They are well-known as n-type semiconductors; so the study of doping with iron, to substitute titanium, and with nitrogen, to substitute oxygen, shows a change from n-type to p-type, and a reduction of the band gap. The physical and chemical properties of the synthetized electrodes were characterized (crystal structure, morphology, optical and photoelectrochemical properties) and discussed according to the composition and synthesis parameters. This work enables to obtain original, efficient, and stable over time, photocathodes (protected copper oxides) and to demonstrate the potential use of doped perovskites for this application

Les bioverres du système quaternaire SiO2-CaO-Na2O-P2O5 obtenus par fusion doivent être coulés à 1400°C, ce qui ne permet pas la mise en forme de matériaux complexes comme par exemple des composites macroporeux en biocéramiques (HA et TCP) recouverts d’une couche uniforme de bioverre. Pour contourner cette limitation, la voie sol-gel a été utilisée dans cette étude. Le but principal a été de synthétiser par le procédé sol-gel, deux compositions quaternaires du système SiO2-CaO-Na2O-P2O5 habituellement obtenues par fusion. Il s’agit des compositions 45S5® de L.L. Hench et 47Q de C. Duée. Ces verres sont inversés, c’est à dire qu’ils contiennent plus d’éléments modificateurs (calcium et sodium) que d’éléments formateurs (silicium et phosphore). Pour la synthèse sol-gel, du TEOS (TétraEthylOrthoSilicate) et du TEP (TriEthylPhosphate) ont été utilisés pour introduire les formateurs. En utilisant des précurseurs minéraux pour le calcium et le sodium, il existe des difficultés à maintenir le gel amorphe lors de son séchage. En effet, les précurseurs minéraux sont le siège de mécanismes de dissolution-précipitation liés entre autres aux solvants choisis, à la nature et à la concentration des anions dans le milieu. L’étude s’est donc orientée vers l’utilisation d’autres précurseurs des modificateurs afin de limiter la part des anions qui contribuent au phénomène de précipitation non souhaité. Deux procédés de synthèse originaux ont été alors mis au point avec des précurseurs alcoolates, acétates et du glycérol. Avec ces procédés, la nature amorphe des composés a été confirmée et leurs caractéristiques thermiques ont été ensuite étudiées. Tous les verres sol-gel réalisés sont bioactifs. Les compositions de base, 45S5® et 47Q, ont été ensuite dopées avec de l’argent afin de doter les bioverres d’une action antibactérienne. Des cellules L132 ont été utilisées pour évaluer la toxicité des poudres des deux procédés solgel. Le procédé le moins toxique a été conservé pour la suite de l’étude. Les bioverres dopés et non dopés ont été alors déposés à la surface d’échantillons plats et macroporeux en HA et TCP par une technique de trempage-retrait. Des tests de prolifération et de formation de biofilms par Pseudomonas aeruginosa ont été réalisés sur des pastilles de TCP recouvertes et ont mis en évidence un effet toxique des dépôts contenant de l’argent. Des mesures de prolifération et de vitalité sur des cellules humaines MG63 ont été également réalisées et ont permis d’observer également un effet toxique. Cet effet n’est pas souhaitable dans ce cas car il affecte la biocompatibilité de l’implant. Il devrait cependant être confirmé par d’autres tests réalisés avec d’autres lignées cellulaires
Bioglasses of quaternary system SiO2-Na2O-CaO-P2O5 obtained by melting are cast at 1400 ° C, which does not allow the shape of complex materials, for example macroporous bioceramics composites (HA and TCP) coated with an uniform layer of bioglass. To overcome this limitation, the sol-gel process has been used in this study. The aim has been to synthesize by sol-gel process, two quaternary compositions usually obtained by melting in the SiO2- CaO-Na2O-P2O5 system. These are two compositions: 45S5® of L.L. Hench and 47Q made by C. Duée. These glasses are reversed, ie they contain more modifiers elements (calcium and sodium) as formers elements (silicon and phosphorus). For the sol-gel synthesis, TEOS (TetraEthylOrthoSilicate) and TEP (TriEthylPhosphate) have been used to introduce the formers. When minerals precursors are used for calcium and sodium, there are difficulties to maintain amorphous the gel during its drying. Indeed, minerals precursors have some dissolution-precipitation mechanisms linked to the selected solvents and the nature and concentration of anions in the medium. The use of other modifiers precursors has been made in the study to limit the proportion of anions contributing to the undesired precipitation phenomenon. Two original synthesis methods have been developed with alkoxide precursors, acetates and glycerol. With these processes, the amorphous nature of the compounds has been confirmed and their thermal characteristics have been studied. All sol-gel glasses are bioactives. The compositions, 45S5® and 47Q, have been doped with silver to add an antibacterial action to the bioglasses. L132 cells have been used to test the toxicity on the powders of the two sol-gel processes. The least toxic process is has been retained for the other tests. Doped and undoped bioglasses have been coated on the surface of flat and macroporous samples of HA and TCP by a dip-coating technique. Proliferation tests and biofilms formation by Pseudomonas aeruginosa have been made on coated TCP and show toxic effects of silver. Proliferation and vitality tests have been also made on MG63 human cells and have allowed to observe a toxic effect. This effect is not suitable in this case because it affects the biocompatibility of the implant. It would, however, be confirmed by other tests with other cell lines

A grande variedade de propriedades dos óxidos com estrutura perovskita permite sua aplicação em diversas áreas da tecnologia. Em especial, as propriedades eletroquímicas e a estabilidade térmica de alguns destes compostos faz destes materiais os mais usados em cátodos de dispositivos para geração de energia como as células a combustível de óxido sólido (SOFC). As SOFC são dispositivos que podem atingir altas eficiências na conversão de energia elétrica e são passíveis de utilização na geração de energia sustentável e distribuída. Para estas células, as perovskitas compostas de manganita de lantânio dopada com estrôncio (LSM) preenche a maioria dos requisitos para aplicação como cátodos da SOFC. Nas células a combustível de óxido sólido de temperatura intermediária (IT-SOFC) há a possibilidade de construir a célula com filmes finos dos materiais cerâmicos suportados em um interconector metálico. No entanto, para os cátodos das IT-SOFC as manganitas não possuem bom desempenho eletroquímico devido à menor temperatura de operação do dispositivo, sendo necessário o desenvolvimento de condutores mistos para aumentar os sítios reativos para reação de redução do O2. Assim, o desenvolvimento de cátodos utilizando a perovskita cobaltita de estrôncio dopada com antimônio (SCS) tem sido proposto para esta aplicação. Portanto, a execução deste trabalho visou à obtenção tanto da LSM quanto da SCS que são materiais para SOFC e IT-SOFC, respectivamente. A LSM também foi avaliada frente a condições de processamento e sinterização. Os pós de LSM foram obtidos através da síntese por combustão, variando a quantidade e tipo de combustível atentando aos aspectos morfológicos resultantes dos parâmetros selecionados. O método de sol-gel foi testado para obtenção da LSM, para fins comparativos. O método de combustão também foi utilizado para obter a SCS, observando a influência do tempo de calcinação sobre a formação das fases. Os pós das manganitas que apresentaram as características mais promissoras foram depositados sobre substratos densos de zircônia estabilizada com ítria (YSZ), na forma de filmes finos pela técnica de dip coating. A perovskita LSM pôde ser obtida de forma monofásica após calcinação e o resultado final da formação da estrutura romboédrica não foi alterado em função do excesso e do tipo de combustível ou do método de síntese utilizado. Agregados com morfologia distinta, formados por partículas nanocristalinas com tamanho médio de aproximadamente 30 nm, foram observados quando a sacarose foi utilizada como combustível e também quando misturada na solução precursora com ureia, formando cristalitos com tamanho médio próximo a 20 nm. A sacarose também promoveu a obtenção do pó de maior área superficial específica (34,9 m²/g) que apresentou taxas de sinterização mais elevadas que os outros pós. As deposições da LSM sobre a YSZ formou filmes contínuos quando os substratos utilizados possuíam rugosidade intermediária e também quando as deposições iniciais foram feitas utilizando baixas velocidades de retirada do banho. O uso de uma solução à base de água destilada com alto teor de ligantes promoveu a obtenção de um filme fino de 3 μm e com uma microestrutura porosa. A síntese por combustão também possibilitou a obtenção da perovskita SCS, no entanto após 6 horas de calcinação o pó ainda apresentou fases secundárias e maiores tempos podem ser necessários para a obtenção de um material monofásico. O alto calor da síntese do pó de SCS formou agregados densos, porém nanocristalinos.
The great variety of properties of oxides with the perovskite structure allows their application in several fields of technology. Specially, the electrochemical properties and the thermal stability of some of these compounds make these materials the most used in devices for energy generation such as the solid oxide fuel cells (SOFC). SOFC’s are devices the reach high efficiencies in the conversion of electric energy and are likely to be used in sustainable and distributed energy generation. For this cells, perovskitas composed by strontium doped lanthanum manganites (LSM) is the material that fits most of requirements for the application in SOFC’s cathodes. In the intermediate temperature solid oxide fuel cells (IT-SOFC) there is the possibility to build a cell with thin ceramic films supported in a metallic interconnector. However, for IT-SOFC’s cathodes, LSM no longer has a good electrochemical performance due to the device’s lower operating temperatures, being necessary the development of mixed conductors to increase the amount of reactive sites for the reduction of O2. In this context, the development of cathodes based on antimony doped strontium cobaltites (SCS) perovskites is being proposed to this application. This work was executed looking for the obtaining of LSM, a material for SOFC cathodes, and to evaluate its behavior against processing conditions; and for the obtaining of SCS, a material for IT-SOFC cathodes. LSM powders were obtained by combustion synthesis, varying the amount and type of fuel, and observing the resulting morphological aspect conferred by the selected parameters. For comparison, the obtaining of LSM powders was carried out via the sol-gel method. The combustion method was also used for the obtaining of SCS, watching for the calcination time. LSM powders were processed and powder with most promising characteristics was used in dispersions for dip coating of dense YSZ substrates. The LSM perovskite was obtained as a single phase powder after calcination without influence of the fuel excess, fuel type or synthesis method, in the final formation of the rhombohedral structure. Aggregates with distinct morphology, formed by nanocrystalline particles with average size around 30 nm, were observed when sucrose was used as fuel and also when mixed with urea in the precursor solution, which formed crystallites with average size near 20 nm. The use of sucrose also promoted the obtaining of the powder with the higher specific surface area (34,9 m²/g) which presented sintering rates higher than the other powders. When not too rough, the YSZ substrates had more continuous films formed in its surface and also when the first depositions were made with the substrates slowly emerging from the bath. The use of a solution based on distilled water with higher amount of binder, promoted the obtaining of films as thin as 3 μm and with a porous microstructure. Combustion synthesis also led to the obtaining of the SCS perovskite, however after 6 hours calcination the powder still presented secondary phases and longer calcination periods may be necessary for the obtaining of a single phase material. The high heat of the SCS synthesis reaction formed dense, yet nanocrystalline aggregates.

Le travail de thèse porte sur les méthodes de synthèse de nanostructures de dioxyde de titane et de leurs études physicochimiques afin de préciser les corrélations entre la morphologie, le dopage métallique, les caractéristiques structurales avec l'efficacité photocatalytique. Le grand intérêt pour les nanomatériaux TiO2 réside dans la mise au point de nouvelles sources d'énergie ou la conservation de l’environnement par des processus photocatalytiques. Cependant, la limitation principale de TiO2 est du au large gap électronique (eV ~3,2) du polymorphe Anatase. Ainsi, un des objectifs importants pour l'amélioration de l’efficacité des nanomatériaux TiO2 est d'augmenter leur photoactivité en décalantla création de paires d'électron-trou de l’UV à la gamme du visible. D'ailleurs, on a montré que l'utilisation de nanostructures 1D de TiO2 (nanotubes) a amélioré la collection de charges, en favorisant leur transport dans les structures 1D, qui par conséquent réduit au minimum la recombinaison et prolonge les durées de vie des électrons.La première partie de ce travail est dédiée à la synthèse des nanopoudres TiO2 dopées par des ions métalliques (Ag, Cu, Eu) préparés par sol-gel. Même avec différents éléments de dopage qui apparemment peuvent adopter le même état de valence (2+) (Cu2+, Ag2+, Eu2+), différents comportements ont été démontrés pour l'incorporation efficace de ces ions dans la structure de TiO2. L'anomalie entre les rayons ioniques des différents éléments utilisés module le rapport du dopage substitutionnel. Ceci est en effet réalisé pour Cu2+ mais dans moins d'ampleur pour Ag2+ tandis que les ions d'europium forment une ségrégation de phase Eu2Ti2O7. La dégradation de colorants de bleu de méthylène (MB) a étéaméliorée légèrement avec les échantillons dopés Ag. La raison a été attribuée aux clusters métalliques Ag qui ont été en effet mis en évidence à travers leur bande d’absorption plasmonique. La deuxième partie porte sur des couches minces de TiO2 dopés (Cu, Ag, et Eu) qui ont été élaborés par sol-gel et spin-coating et dipcoating. Les paramètres optimaux ont été obtenus pour réaliser les films cristallins mais présentant une organisation mésoporeuse qui dépend également du processus de dopage. Des études de Photocatalyse ont été également réalisées et l'efficacité des films ont été comparées en fonction des éléments dopants. La troisième partie de la thèse est liée à la modification morphologique des nanoparticules pour former des nanotubes à l'aide de la méthode hydrothermale sous pression contrôlée. Un plan d'expérience basé sur la méthode Taguchi a été utilisé pour la détermination des paramètres optimaux.Les nanotubes TiO2 augmentent la surface spécifique en comparaison avec les nanoparticules. La dégradation de bleu deméthylène par les nanotubes a montré une efficacité photocatalytique plus élevée qu’avec les nanopoudres TiO2 pures etdopés Ag
The thesis work is focused on the synthesis methods of titanium dioxide nanostructures and their physico-chemical studies in order to point out the correlations between the morphology, metal doping, structural features with the photocatalytic efficiency. The great interest on TiO2 nanomaterials deals with new sources of energy or in the environment preservation through the photocatalytic properties. However, the main limitations is due to the wide band gap (~3.2 eV) of the anatase polymorph. Thus, a major objective for improvement of the performance of TiO2 nanomaterials is to increase theirphotoactivity by shifting the onset of the electron-hole pairs creation from UV to the visible range. Moreover, it was found that using onedimensional (1-D) TiO2 (nanotubes) improved the charge collection by 1D nanostructures which consequently minimizes the recombination and prolongate the electron lifetimes. The first part of this work is focused on the synthesis of TiO2 nanopowders doped with metallic ions (Ag, Cu, Eu) prepared by Solgel. Even with different doping elements which apparently can adopt the same valence state (2+) such as (Cu2+, Ag2+,Eu2+), different behaviors were demonstrated for the effective incorporation of these ions in the host structure of TiO2. The discrepancy between ionic radii of the different used elements modulates the ratio of the substitutional doping. This is indeed achieved for Cu2+ but in less extent for Ag2+ while Europium ions form segregated phase as Eu2Ti2O7. The experiments on the degradation of methylene blue (MB)dyes have shown slight improvement with Ag-doped samples. The reason was tentatively attributed to the Ag clusters which were indeed demonstrated through their plasmon optical band. The second part of the work concerns thin films of TiO2 doped (Cu, Ag, and Eu) which were elaborated by spin coating and dip coating. The optimal parameters were obtained to achieve crystalline films but presenting mesoporous organisation which also depends on the doping process. Photocatalysis investigations were also realized and the efficiency of the films compared as function of the doping elements.The third part of the thesis is related to the morphological modification from nanoparticles to nanotubes by using the hydrothermal method with controlled pressure. An experimental design based on Taguchi Method was employed for the determination of the optimal parameters. TiO2 nanotubes increase the surface area in comparison with TiO2nanoparticles. TiO2 nanotubes were tested for the methylene blue degradation and show a higher photocatalytic efficiency than TiO2 nanopowders and TIO2 doped with Ag

The work deals with the deposition of layers for electrochromic device with different methods. Transparent electrically conductive layer of SnO2 was deposited by pyrolytic decomposition of peroxostannate solution. Hydrogen peroxide in starting solution contributes to the oxidation process of growth layers and to increase the electrical conductivity. Active electrochromic layer of WO3 was electrolytic deposited from the peroxotungstic acid solution. Optimal deposition time and the optimal annealing temperature of deposited layers were found. Passive electrochromic layer of V2O5 was deposited using dip-coating method from peroxovanadate solution. A contribution of solution diluted with distilled water was investigated. Found results were used to construct complete electrochromic device with polymer gel electrolyte.

碩士
大華科技大學
機電研究所
107
In recent years, with the sale of Apple's smart phones (i-Phone) and tablet com-puters (i-Pad), touch products have not been converted from high-end to basic func-tions, and various manufacturers have introduced various touches. Products have come to each other, causing 3C product manufacturers to contend. The "touch" func-tion of 3C products, such as Anti-Reflection Film (AFM), insulating film, conductive film, Hard Coating, Anti-Smudge, etc. The control functions are related to the pro-cess parameters of the overall use of the film, and with the increasing demand for touch film functions, we have to pay attention to the overall process of the touch film. Since the light passes through the surface of the glass or plastic substrate, such as PET, PC, etc., the surface of the medium will have a reflectivity of 4 to 5%, which causes the user to be easily disturbed by external light when using the display, and sees that some are not or changed. Create an image of the outer boundary. At this time, if the anti-reflection film treatment can be performed on the surface of the glass or plastic substrate, it is the best way to solve the light reflection. General an-ti-reflective film treatment can reduce the interference of glass or plastic substrate on external light, and can improve the light transmittance and color contrast of glass or plastic substrate components, thereby improving the user's comfort for 3C products. In addition to the reflectivity requirements of glass or plastic substrates, an-ti-reflective coatings also require properties such as penetration, hardness, adhesion, and weather resistance. Due to the high difficulty in making optical films on plastic substrates, only a few companies or R&D institutions in foreign countries have this production capability technology. In view of this, this study aims to apply an-ti-reflective coating on the surface of plastic substrate by sol-gel dipping method to find the best anti-reflective film treatment solution.

博士
逢甲大學
材料科學與工程學系
104
Functional oxide films with thickness from a few tens of nanometers to several hundred micrometers exhibiting special properties are widely applied in industries. These include transparent conducting oxides (TCO) which make insulating glasses conducting and transparent. They may also include hard and hermetic oxide coatings on relatively soft metals such as Al, Mg and Ti and their alloys. The purposes of this study are to explore the two extremes of surface modification, i.e., TCO by dip-coating and protective oxides by micro-arc oxidation. For TCO studies, our concerns are the effects of dopant on the structure, optical transmittance, electrical conductivity and in particular the change in conduction type of tin oxide film as deposited on a glass substrate. For MAO coating we explore factors such as power supply, additives or treatment time on properties of mechanical, corrosion resistance and tribology of ceramic coatings on 6061 Al alloy. The TCO systems investigated in this dissertation were boron doped tin oxide (BTO), fluorine doped tin oxide (FTO) and neodymium-fluorine doped tin oxide (NFTO) films. For BTO films, conduction type changes from n- (un-doped) to p- (1–4 at.% B), then to n-types (5 at.% B), as evidenced from Hall-effect and Seebeck-effect measurements. This is explained by doping-generated defects and phase separations of Sn3O4 and B2O3. The essence of FTO films was the preparation by using a green sol–gel dip-coating process, using non-toxic SnF2 as fluorine source to replace conventional toxic HF or NH4F. Effect of SnF2 content, 0–10 mol%, on structure, electrical resistivity, and optical transmittance of the films were investigated and discussed. Transparent p-type conducting oxide films with high conductivity and transparency of neodymium-fluorine doped tin oxide has been discovered for the first time in literature with NdF3 used as both neodymium and fluorine sources. The NFTO film with 2 mol% NdF3 shows the lowest electrical resistivity, 8.2 x 10–3  cm, the highest hole-concentration, 8.96 x 1019 cm–3 and a Hall mobility 9.74 cm2 V–1 s–1. For MAO coatings on 6061 Al alloy, a simple and less reported hybrid voltage (a direct current coupled with an alternative current, DC + AC) as power supply for the MAO process was explored. Comparing with MAO layers obtained by using DC only, the oxide-layer by hybrid voltages is a little thinner, much harder and much more corrosion resistant. In addition, the effect of additives into electrolyte to the properties of MAO coating is investigated. An anomalous layer-thickening occurred when adding ammonia water into the silicate electrolyte. Average coating thickness increases from 44 m (un-added bath) to 135 m (60 mL/L added bath), along with the reduction in number and size of the pores and cracks. This causes a great improvement in corrosion resistance of the coating. In another study, diamond powder (0, 3, 6 and 9 g/L) was used into the electrolyte containing Na2SiO3 and H3BO3. With 6 g/L added content, the MAO coating shows the best performance in wear and corrosion resistance.

碩士
國立高雄科技大學
化學工程與材料工程系
107
Polymethyl Methacrylate (PMMA) is commonly used in materials such as lenses and lampshades that are exposed to the outside for a long time. If placed outdoors, long-term feeling of various weather changes, rain drops, dust particles stacked on the surface of the polymethyl methacrylate cause visual pollution, or damage the material itself. If PMMA can be self-cleaning and anti-fogging, it will be a big help. Therefore, in this study high transmittance and high adhesion of composite films constituted by TiO2- SiO2/SiO2/PMMA layers will produce, makes the composite film have anti-fogging and self-cleaning function. First, a series of clean processes by various solvents with ultrasonic wave oscilation were carried out. Then , a SiO2, TiO2-SiO2 and TiO2-SiO2/SiO2 film(s) was coated on the PMMA via sol-gel and dip-coating processes. And compare the surface properties of the film. Finally, the surface properties were tested by photodegrading the composite film with a methylene blue. The results showed that the better clean process of PMMA substrate was by the followings: deionized water →n-hexane/ deionized water (1:1) →deionized water, as well as the lowest water contact angle (56.7) was achieved. The addition of SiO2 film between the TiO2-SiO2 film and the PMMA substrate shows that the substrate can be protected from photocatalysis and aging and the hydrophilicity can be improved, but the super-hydrophilicity is not achieved. Unilluminated water contact angle can be reduced to 12.9,condition to match an acceptable anti-fogging performance . In addition, SEM analysis of TiO2-SiO2/SiO2 composite film showed fine surface porosity,and the roughness is 0.045 nm (RMS). The chemical bond was analyzed by XPS to show that the composite film was an amorphous structure, so the photocatalysis was not obvious.

碩士
國立成功大學
材料科學及工程學系
89
Our environment has suffered damage as the economic expands. In order to improve the drawbacks of expensive, heavy and time-consuming in traditional gas sensors, many studies have been focused on thin film gas sensor recently. WO3 thin films were deposited on Al2O3 substrate as gas sensor by sol-gel process in this study. The effects of annealing temperature and Ti dopant on the structure of WO3 were investigated by X-ray diffraction, SEM, TEM and Raman spectroscopy analyses. Sensor properties for NO2 were also investigated. WO3 film is characterized with distorted monoclinic structure. The grain size of 33.8nm calculated from XRD result were obtained after annealing at 400℃ for 1 hr. The degree of distortion decreased with reduced grain size as annealing temperature increased. The sensitivity for NO2 depends on the operation temperature, which has a maximum value at 200℃ with good reproductivity and stability. For titanium dopant effects on the properties of WO3, the structure of WO3 films was distorted and grain growth was inhibited. The sensitivity of WO3 film for sensing NO2 increased with Ti contents, reaching a maximun as Ti/(Ti+W) = 8.7at%. The sensitivity of WO3 film with Ti/(Ti+W) = 19.4at% was 1768 for 10ppm NO2 at 200℃, which was 21.6 times of WO3 sensor tested in the same conditions.

碩士
義守大學
材料科學與工程學系碩士班
99
In this study, the Al/Ga doped ZnO transparent conducting films were fabricated by sol-gel dip coating method. At first, we studied the effect of the processing parameters (withdrawal speed and bath temperature), doping elements (Al,Ga,Al/Ga), and doping amount on microstructure, resistivity and transmittance of the doped ZnO films. The mobility and carrier concentration measurements were used to probe the mechanism of the conductivity. In addition, thermal stability of the doped ZnO films was further explored in details. The results indicated that the withdrawal speed significantly influenced the film thickness, whereas did not change the particle size of films. The film thickness increased with decreasing the bath temperature, this was contributed to the fact that the viscosity of the bath decreased with temperature. For transmittance of films, the withdrawal speed and bath temperature were not major factors, it was mostly decided by the film thickness. When doping with 1.5 mol% Al and 1.95 mol% Ga, the ZnO films had the lowest resistivity of 1.07 × 10-2 Ω-cm and 7.88 × 10-3 Ω-cm, respectivity. Carrier concentration increased with Al or Ga doping amount. As the doping amount of Al and Ga was increased to 1.5 mol% and 1.95 mol%, the carrier concentration became saturated; on the other hand, the Hall mobility would increase with the increasing of dopant content. After 150 ℃ heat treatment for 30 min in air, the carrier concentration of ZnO films apparently decreased with the doping content. This is due to the fact that the more the doping amount, the more the doping ions would be oxidized or the original oxygen vacancies would be refilled. This led to the decrease of carrier concentration and the increase of resistivity. The thermal stability of Ga-doped ZnO films was higher than that of Al-doped ZnO films. The ZnO films doped with higher amount exhibited a higher transmittance owing to the Burstein-Moss shift. In addition, when the ZnO films were doped 3.25-3.9 mol% Ga, some cracks were observed resulting in the decrease of the transmittance. For Ga/Al codoped ZnO films, the carrier concentration and mobility increased with Ga-doped amount, whereas resistivity decreased and transmittance increased with Ga-doped amount. After 150 ℃ heat treatment in air for 30 min, the carrier concentration remained unchanged and the Hall mobility decreased with the increasing of Al-doped content. At high relative humidity of 65%-75% and the higher film thickness (> 1800nm), the film surface often presented the sheet structure particles, which resulted in the increase of roughness and resistivity, and the decrease of transmittance.

碩士
國立中正大學
化學工程研究所
92
Preparation the porous SiO2 thin film by sol-gel dip-coating technique and supercritical carbon dioxide drying process has been studied in this research. During removing the residual liquid away from porous thin film, the process of supercritical drying prevents the micro structures from collapse. Several operating parameters of the supercritical drying process have been investigated to understand the pores size and thin film morphology for the future application on the immobilization of enzyme. First of all, increasing the R value (the molar ratio of H2O to Si) has the positive effect on the gelation rate at pH=8. Comparing four drying methods (i.e., solvent exchange with supercritical drying, supercritical drying, freeze-drying, and hot drying), results showed that the solvent exchange with supercritical drying has less shrinkage and the biggest pore. Then, orderly the supercritical drying, the freeze drying, and the hot drying have the different level of shrinkage and pore size. The hot drying has the serious collapse of the micro structure. Secondly, under the same time of ambient dip-coating and supercritical drying, it is found that 1) the increase of aging time can obtain thicker and less roughness of thin film; 2) the fast venting rate has serious issues on shrinkage and less specific surface area. For example, during the dip-coating time between 65 and 85 minutes, the specific surface areas varying from 829 to 1317 m2/g and 683 to 1012 m2/g for the venting rates of 25 and 50psi/min, respectively. On the other hand, the supercritical dip-coating drying could obtain thicker and rougher film than the ambient dip-coating film with supercritical drying. Because of increasing the hydrolysis and condensation rate, the system pressure and the immerse time in the supercritical fluid have a positive influence on the thickness of the film.

碩士
國立臺南大學
材料科學系碩士班
105
TiO2 is one of the most used functional materials for advanced applications. In many studies, TiO2 had been applied to produce self-cleaning windows because of its superior photocatalytic ability and the transparent property of thin films. In this study, TiO2 seed layers on the Si(100) substrate were first prepared by dip-coating method. To increase the crystallinity of TiO2 seed layers, multiple times of dip-coating and heat treatment were utilized. Then, the hydrothermal process was implemented to grow TiO2 nanorods array at 180oC for 2 hours. Finally, the post-heat treatment was applied again on TiO2 nanorods array. The properties of TiO2 seed layers and nanorods array were characterized, and the influence of heat treatment with different parameters on the photocatalytic properties of TiO2 seed layers and nanorods array were also analyzed. The results showed that the crystallinity of TiO2 seed layers was increased with the thickness of thin films. From SEM analysis, it can be found that the TiO2 seed layers coated on the substrate surface were uniform. However, while the TiO2 seed layers were getting too thick, the cracks would appear on the surface of TiO2 films. With the heat treatment at a high temperature, the growth of the TiO2 seed layers was observed, and the crystallinity of the films would be improved. In the experiments of the hydrothermal method, various concentrations of HCl were used to control the morphologies of the TiO2 thin films by virtue of the inhibition of TiO2 hydrolysis in the solution. In SEM images, it was observed that the rectangle shape of TiO2 columns would form in the hydrothermal treatment with high HCl concentration and a flower-like morphology of TiO2 developed in a low HCl concentration. According to the experimental results, the best degradation of the methyl blue solution happened in the 3 layers of TiO2 seed layer. The photocatalytic activity of TiO2 was reduced after the hydrothermal treatment. To improve the photocatalytic properties of TiO2 thin films, a post-heat treatment on TiO2 thin films would be necessary after the hydrothermal treatment.

碩士
國立臺南大學
材料科學系碩士班
104
ZnO thin films are widely used in different applications, because of its direct band gap, high exciton density, tunable conductivity and good chemical stability. Many studies have been published on the ZnO thin films produced by sol-gel method. The procedures are usually involved three or more chemical products, and it always takes a lot of time for aging process. In this study, we adopted a method for shortening the cycle time. Ethanol and zinc acetate dehydrate were used as the precursor for the sol-gel method, and different withdrawal speeds were applied in the dip-coating method, such as 10mm/min, 50mm/min and 100mm/min respectively. Then the ZnO thin films were post-annealed by the atmosphere oven and microwave oven with different temperatures, and the atmosphere plasma with different scanning times. Furthermore, the photocatalytic activities of ZnO thin films was analyzed. As the results, we found that layer-like or sheet-like shape of ZnO thin films were presented when the as-coated films were annealed by atmosphere oven. In the microwave oven process, the spherical particles of ZnO were formed. By the atmosphere plasma treatment, ZnO thin films were modified and transformed into particles with sharp edge. While the ZnO thin films prepared by 50mm/min withdrawal speed accompanying with microwave oven or atmosphere plasma treatment, good photocatalytic performances were carried out. We assumed that increasing withdrawal speed in the dip-coating method, more ZnO particles were adhered to the substrate, and it might leads to create more reaction area of ZnO thin films in the photocatalytic experiments. But when the ZnO thin films appeared in the layer-like or sheet-like morphology, the photocatalytic activities would get worse. It could be attributed to that the by-products of the reaction would attach to the ZnO surface and block the further photocatalytic reaction.